Preparation method and application of metal organic framework catalytic material embedded with metal particles

Abstract

The invention discloses a preparation method and application of a metal organic framework catalytic material embedded with metal particles, relates to the technical field of photo-thermal catalytic materials, and aims at solving the technical problems that an existing supported metal type solid catalyst is relatively low in selective hydrogenation activity on furfural and high in preparation cost. The preparation method of the metal organic framework catalytic material comprises the following steps: obtaining a metal target sheet; the preparation method comprises the following steps: placing a metal target sheet in N, N-dimethylformamide, and irradiating the metal target sheet by using a pulse laser beam under an ultrasonic condition to obtain a monometal precursor solution with the metal content of 0.05-0.4 wt%; mixing the at least two monometal precursor solutions to obtain a multi-metal precursor solution; the preparation method comprises the following steps: uniformly dispersing a metal salt and an organic ligand in a multi-metal precursor solution, adding glacial acetic acid and ultrapure water, carrying out solvent heat treatment at 100-120 DEG C for 12-24 hours, and cooling to obtain the metal organic framework catalytic material.

Description

Technical Field

[0001] The present invention relates to the technical field of photo-thermal catalytic materials, and more specifically, to a preparation method and application of a metal organic framework catalytic material embedded with metal particles. Background Art

[0002] Catalytic transfer hydrogenation plays a vital role in the high-value conversion of bio-derived platform molecules. For example, the use of hydrogen-donating solvent molecules can achieve high-value utilization of biomass derivatives under relatively mild conditions. Furfural (FAL), as a lignin derivative and a biomass-derived model molecule containing two different unsaturated functional groups, has attracted widespread attention because of its selective hydrogenation into different high-value-added chemicals and fuels. In recent years, highly active precious metal-based catalysts have made great progress in the liquid-phase furfural hydrogenation reaction of thermal catalysis and photothermal catalysis.

[0003] Porous catalysts with different micro-nano structures, such as metal oxides, molecular sieves, MOFs and other supported catalysts loaded with active metals such as Pd, Pt, and Ru, have been widely studied in the catalytic hydrogenation of furfural, and Pt-based and Pd-based solid catalysts have been widely studied in the hydrogenation of C=O and C=C unsaturated bonds. However, since the loaded precious metals are easily detached from the carrier during use, these supported metal solid catalysts prepared by traditional wet chemical methods have low selective hydrogenation activity for furfural and high preparation costs, which hinders the high-value utilization of biomass resources. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation method and application of a metal organic framework catalytic material embedded with metal particles, which is used to solve the technical problems that the existing supported metal solid catalyst has low selective hydrogenation activity for furfural and high preparation cost. In view of this, the present invention is implemented through the following technical solutions.

[0005] In a first aspect, the present invention provides a method for preparing a metal organic framework catalytic material embedded with metal particles, comprising: Obtain a metal target; The metal target sheet is placed in N,N-dimethylformamide, and a pulsed laser beam is used to irradiate the metal target sheet under ultrasonic conditions to obtain a single metal precursor solution having a metal content of 0.05-0.4 wt %; Mixing at least two of the single metal precursor solutions to obtain a multi-metal precursor solution; After uniformly dispersing metal salts and organic ligands in the multi-metal precursor solution, glacial acetic acid and ultrapure water are added, and solvent thermal treatment is performed at a temperature of 100-120° C. for 12-24 hours. After cooling, a metal organic framework catalytic material is obtained.

[0006] Compared with the prior art, in the preparation method of the metal organic framework catalytic material embedded with metal particles of the present invention, a single metal precursor solution can be obtained by irradiating a metal target sheet with a pulsed laser beam, and the aggregation of metal particles in the solution can be avoided under ultrasonic conditions. A plurality of single metal precursor solutions are mixed to obtain the above-mentioned multi-metal precursor solution; metal salts and organic ligands are uniformly dispersed in the multi-metal precursor solution, and during the solvent thermal treatment, metal ions (provided by metal salts) and organic ligands are combined through coordination bonds to form a metal organic framework material (MOF material) with a network structure, and the metal particles in the multi-metal precursor solution will be embedded in the metal organic framework material in situ, that is, embedded in the material at the metal position of the metal organic framework material, thereby obtaining a metal organic framework catalytic material with good catalytic activity. In the above technical scheme of the present invention, the average particle size of the metal particles is 1~5nm. By integrating the external active sites (metal particles) into the self-structure of the MOF material, the limitation of the narrow reaction area of ​​the MOF material itself is broken through, and the aggregation effect of the active sites (metal particles) caused by insufficient anchoring force can be effectively suppressed. The metal organic framework catalytic material of the present invention is applied to the catalytic transfer hydrogenation reaction of furfural, which can promote the adsorption-activation of the reactant furfural and the hydrogen donor molecule at the active center, thereby significantly broadening the region of the catalytic transfer hydrogenation reaction of the substrate molecule and increasing the reaction rate; the turnover frequency value of furfural can reach 150-430h -1 , which is at least 2 to 8 times higher than the existing solid catalyst. Furthermore, the above technical solution has great universality, high catalyst preparation efficiency, and can use base metals to effectively reduce the synthesis cost of the catalyst, providing a simple, environmentally compatible and low-cost technical solution for biomass resource integration and upgrading. Through the above technical solution of the present invention, the technical problems of low selective hydrogenation activity of existing supported metal solid catalysts for furfural and high preparation cost are solved.

[0007] Furthermore, in the method for preparing the metal organic framework catalytic material embedded with metal particles of the present invention, the mixing of at least two single metal precursor solutions comprises: At least two of the single metal precursor solutions are mixed in equal volumes.

[0008] Furthermore, in the method for preparing a metal-organic framework catalytic material embedded with metal particles of the present invention, the metal target sheet includes a cobalt target sheet and a nickel target sheet.

[0009] Furthermore, in the method for preparing the metal organic framework catalytic material embedded with metal particles of the present invention, in the process of irradiating the metal target sheet with a pulsed laser beam, the pulsed laser beam includes a pulsed unfocused laser beam; The output wavelength of the pulsed laser beam is 1064nm, the pulse frequency is 20-40Hz, the output spot diameter is 5-10mm, and the irradiation energy density of the laser beam is 500-1400mJ / cm 2 The irradiation time is 5 to 10 minutes.

[0010] Furthermore, in the method for preparing a metal organic framework catalytic material embedded with metal particles of the present invention, during the process of irradiating the metal target sheet with a pulsed laser beam, the temperature of N,N-dimethylformamide is -15 to 0 o C, the frequency of ultrasound is 20~40kHz.

[0011] Furthermore, in the method for preparing the metal organic framework catalytic material embedded with metal particles of the present invention, the metal salt comprises zirconium chloride, ferric chloride and hydrated copper nitrate; and / or, The organic ligands include 2-aminoterephthalic acid, terephthalic acid and 2-hydroxyterephthalic acid.

[0012] Furthermore, in the method for preparing the metal organic framework catalytic material embedded with metal particles of the present invention, the mass ratio of the metal salt to the organic ligand is 1:(1-2).

[0013] Furthermore, in the method for preparing the metal organic framework catalytic material embedded with metal particles of the present invention, the metal salt and the organic ligand are uniformly dispersed in the multi-metal precursor solution, comprising: 60-80 mg of metal salt and 80-100 mg of organic ligand are dissolved in 6-12 mL of the multi-metal precursor solution.

[0014] In a second aspect, the present invention provides a metal organic framework catalytic material, which is prepared using the above-mentioned method for preparing a metal organic framework catalytic material embedded with metal particles, and the metal particle content in the metal organic framework catalytic material is 0.1-0.3wt%.

[0015] In a third aspect, the present invention provides the use of the above metal organic framework catalytic material in the catalytic transfer hydrogenation reaction of furfural. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 A schematic diagram of the process flow of the method for preparing a laser-broadened metal organic framework active site region catalyst provided by the present invention; Figure 2 This is a physical picture of Co(DMF) in Example 1 of the present invention; Figure 3 This is a physical picture of Ni(DMF) in Example 1 of the present invention; Figure 4 This is a sample photo of CoNi@MOF in Example 1 of the present invention; Figure 5 Schematic diagram of the SEM and element distribution of CoNi@MOF in Example 1 of the present invention; wherein, FIG. a is a SEM morphology of the MOF material at low resolution, FIG. b is a SEM morphology of CoNi@MOF at low resolution, FIG. c is a superposition of C, N, Zr, Co and Ni elements in CoNi@MOF, FIG. d is a schematic diagram of the carbon element distribution in CoNi@MOF, FIG. e is a schematic diagram of the oxygen element distribution in CoNi@MOF, FIG. f is a schematic diagram of the nitrogen element distribution in CoNi@MOF, FIG. g is a schematic diagram of the zirconium element distribution in CoNi@MOF, FIG. h is a schematic diagram of the cobalt element distribution in CoNi@MOF, and FIG. i is a schematic diagram of the nickel element distribution in CoNi@MOF; Figure 6 TEM and element distribution diagram of CoNi@MOF in Example 1 of the present invention; wherein, Figure a is a TEM schematic diagram of CoNi@MOF, Figure b is a schematic diagram of oxygen element distribution in CoNi@MOF, Figure c is a schematic diagram of zirconium element distribution in CoNi@MOF, Figure d is a schematic diagram of cobalt element distribution in CoNi@MOF, and Figure e is a schematic diagram of nickel element distribution in CoNi@MOF; Figure 7 Schematic diagram of the performance of catalytic transfer hydrogenation of furfural by CoNi@MOF catalyst in hydrogen donor solvent in Example 1 of the present invention. DETAILED DESCRIPTION

[0017] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0018] It should be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it can be directly on the other element or indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or indirectly connected to the other element.

[0019] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined. The meaning of "several" is one or more, unless otherwise clearly and specifically defined.

[0020] Porous catalysts with different micro-nano structures, such as metal oxides, molecular sieves, MOFs and other supported catalysts loaded with active metals such as Pd, Pt, and Ru, have been widely studied in the catalytic hydrogenation of furfural, and Pt-based and Pd-based solid catalysts have been widely studied in the hydrogenation of C=O and C=C unsaturated bonds. However, since the loaded precious metals are easily detached from the carrier during use, these supported metal solid catalysts prepared by traditional wet chemical methods have low selective hydrogenation activity for furfural and high preparation costs, which hinders the high-value utilization of biomass resources.

[0021] In order to solve the above technical problems, in a first aspect, the present invention provides a method for preparing a metal organic framework catalytic material embedded with metal particles, comprising: Obtain a metal target; The metal target sheet is placed in N,N-dimethylformamide, and a pulsed laser beam is used to irradiate the metal target sheet under ultrasonic conditions to obtain a single metal precursor solution having a metal content of 0.05-0.4 wt %; Mixing at least two of the single metal precursor solutions to obtain a multi-metal precursor solution; After uniformly dispersing metal salts and organic ligands in the multi-metal precursor solution, glacial acetic acid and ultrapure water are added, and solvent thermal treatment is performed at a temperature of 100-120° C. for 12-24 hours. After cooling, a metal organic framework catalytic material is obtained.

[0022] In the case of adopting the above technical scheme, in the preparation method of the metal organic framework catalytic material embedded with metal particles of the present invention, a single metal precursor solution can be obtained by irradiating a metal target sheet with a pulsed laser beam, and the aggregation of metal particles in the solution can be avoided under ultrasonic conditions. A plurality of single metal precursor solutions are mixed to obtain the above multi-metal precursor solution; metal salts and organic ligands are uniformly dispersed in the multi-metal precursor solution, and during the solvent thermal treatment, metal ions (provided by metal salts) and organic ligands are combined through coordination bonds to form a metal organic framework material (MOF material) with a network structure, and the metal particles in the multi-metal precursor solution will be embedded in the metal organic framework material in situ, that is, embedded in the material at the metal position of the metal organic framework material, thereby obtaining a metal organic framework catalytic material with good catalytic activity. In the above technical scheme of the present invention, the average particle size of the metal particles is 1~5nm. By integrating the external active sites (metal particles) into the self-structure of the MOF material, the limitation of the narrow reaction area of ​​the MOF material itself is broken through, and the aggregation effect of the active sites (metal particles) caused by insufficient anchoring force can be effectively suppressed. The metal organic framework catalytic material of the present invention is applied to the catalytic transfer hydrogenation reaction of furfural, which can promote the adsorption-activation of the reactant furfural and the hydrogen donor molecule at the active center, thereby significantly broadening the region of the catalytic transfer hydrogenation reaction of the substrate molecule and increasing the reaction rate; the turnover frequency value of furfural can reach 150-430h -1 , which is at least 2 to 8 times higher than the existing solid catalysts. Furthermore, the above technical solution has great universality, high catalyst preparation efficiency, and can use base metals to effectively reduce the synthesis cost of the catalyst, providing a simple, environmentally compatible and low-cost technical solution for the integration and upgrading of biomass resources. Through the above technical solution of the present invention, the technical problems that the existing loaded metal solid catalysts have low selective hydrogenation activity for furfural and high preparation cost are solved. In the above technical solution, for example, at least two single metal precursor solutions can be mixed in equal volumes, the metal target sheet includes a cobalt target sheet and a nickel target sheet, and the temperature of the solvent thermal treatment can be 100°C, 110°C or 120°C, and the time can be 12 hours, 18 hours or 24 hours.

[0023] It should be noted that in the above technical solution, glacial acetic acid and ultrapure water are added to the multi-metal precursor solution, and the glacial acetic acid aqueous solution is used as a catalyst, which can significantly increase the solvent thermal treatment rate and improve the preparation efficiency of the metal organic framework catalytic material. After obtaining the metal target sheet, the type of metal target sheet required can be selected according to the design principle of the base metal active center, and the metal target sheet is ultrasonically cleaned to remove the oxide layer or impurities that may exist on the surface of the metal target sheet. The frequency of ultrasound during ultrasonic cleaning can be 10kHz, and the cleaning time can be 30 minutes. After completing the ultrasonic cleaning, the metal target sheet can also be placed in N,N-dimethylformamide (DMF) and laser pre-treated to further remove the oxide layer and impurities that may exist on the surface of the metal target sheet. For the above-mentioned metal target sheet, its purity is required to reach 99.9999%.

[0024] It should be understood that in the preparation method of the metal organic framework catalytic material embedded with metal particles of the present invention, in the process of irradiating the metal target sheet with a pulsed laser beam, by selecting a pulsed laser beam, or controlling the irradiation parameters of the pulsed laser beam, and the irradiation time, on the one hand, the particle size of the metal particles can be controlled within a reasonable range (1-5 nm), and on the other hand, the content of the metal particles in the single metal precursor solution can be controlled within a reasonable range (0.05-0.4 wt %); illustratively, the pulsed laser beam includes a pulsed unfocused laser beam; the output wavelength of the pulsed laser beam is 1064 nm, the pulse frequency is 20-40 Hz, the output spot diameter is 5-10 mm, and the irradiation energy density of the laser beam is 500-1400 mJ / cm 2 , the irradiation time is 5 to 10 minutes. In another example, the pulse frequency can be 20 Hz, 30 Hz or 40 Hz, and the output spot diameter can be 5 mm, 5 mm or 10 mm. The irradiation energy density of the laser beam can be 500 mJ / cm 2 、1200mJ / cm 2 or 1400mJ / cm 2 The irradiation time may be 5 minutes, 8 minutes or 10 minutes. The particle size of the metal particles may range from 1 nm, 3 nm or 5 nm, and the content of the metal particles in the single metal precursor solution may be 0.1 wt%, 0.15 wt% or 0.2 wt%.

[0025] It should also be understood that, as described above, under ultrasonic conditions, the aggregation of metal particles in the solution (single metal precursor solution) can be avoided. In order to further disperse the metal particles more evenly in N,N-dimethylformamide, the process of irradiating the metal target sheet with the laser beam can be controlled at a low temperature. For example, the frequency of the ultrasound can be 20 to 40 kHz, and the temperature of the N,N-dimethylformamide can be -15 to 0 oC. As another example, the frequency of ultrasound can be 20 kHz, 30 kHz or 40 kHz, and the temperature of N,N-dimethylformamide can be -15 o C. -10 o C or 0 o C.

[0026] It should also be understood that in the preparation method of the metal-organic framework catalytic material embedded with metal particles of the present invention, different types of metal-organic framework materials can be obtained by selecting different metal salts and organic ligands, and after the metal particles are embedded in situ, different types of metal-organic framework catalytic materials can be obtained; illustratively, the metal salts include zirconium chloride, ferric chloride and hydrated copper nitrate, and the organic ligands include 2-aminoterephthalic acid, terephthalic acid and 2-hydroxyterephthalic acid; as another example, the metal salts can be zirconium chloride, ferric chloride and hydrated copper nitrate, and the organic ligands can be 2-aminoterephthalic acid, terephthalic acid and 2-hydroxyterephthalic acid. Furthermore, the types and ratios of the metal salt and the organic ligand have a decisive effect on the final structure of the metal organic framework material. The structure of the metal organic framework material further determines its function or performance. Therefore, in order to further improve the catalytic activity of the metal organic framework catalytic material of the present invention, the mass ratio of the metal salt and the organic ligand should also be controlled within a reasonable range. For example, the mass ratio of the metal salt and the organic ligand can be 1: (1~2). For another example, the mass ratio of the metal salt and the organic ligand can be 1:1, 1:1.5 or 1:2. Furthermore, the multi-metal precursor solution serves as a self-assembled liquid environment for metal nodes (metal salts) and organic linkers (organic ligands). Its content, or the amount of metal salts or organic linkers added to the multi-metal precursor solution, will affect the efficiency of the solvent thermal treatment. Therefore, the amount of the multi-metal precursor solution used should also be controlled within a reasonable range. For example, based on the amount of metal salts or organic ligands added, 60 to 80 mg of metal salts and 80 to 100 mg of organic ligands can be dissolved in 6 to 12 mL of the multi-metal precursor solution. For another example, the amount of the multi-metal precursor solution used can be 6 mL, 8 mL or 12 mL, the amount of metal salts added can be 60 mg, 70 mg or 80 mg, and the amount of organic ligands added can be 80 mg, 90 mg or 100 mg.

[0027] In a second aspect, the present invention provides a metal organic framework catalytic material, which is prepared using the above-mentioned method for preparing a metal organic framework catalytic material embedded with metal particles, and the metal particle content in the metal organic framework catalytic material is 0.1-0.3wt%.

[0028] In the case of adopting the above technical scheme, the metal organic framework catalytic material of the present invention is prepared by the above method for preparing the metal organic framework catalytic material embedded with metal particles. In the preparation method of the metal organic framework catalytic material, a single metal precursor solution can be obtained by irradiating a metal target sheet with a pulsed laser beam, and the aggregation of metal particles in the solution can be avoided under ultrasonic conditions. A plurality of single metal precursor solutions are mixed to obtain the above multi-metal precursor solution; metal salts and organic ligands are uniformly dispersed in the multi-metal precursor solution, and during the solvent thermal treatment, metal ions (provided by metal salts) and organic ligands are combined through coordination bonds to form a metal organic framework material (MOF material) with a network structure, and the metal particles in the multi-metal precursor solution will be embedded in the metal organic framework material in situ, that is, embedded in the material at the metal position of the metal organic framework material, thereby obtaining a metal organic framework catalytic material with good catalytic activity. In the above technical solution of the present invention, the average particle size of the metal particles is 1-5 nm. By integrating the external active sites (metal particles) into the structure of the MOF material itself, the limitation of the narrow reaction area of ​​the MOF material itself is broken through, and the aggregation effect of the active sites (metal particles) caused by insufficient anchoring force can be effectively suppressed. The metal organic framework catalytic material of the present invention is applied to the catalytic transfer hydrogenation reaction of furfural, which can promote the adsorption-activation of the reactant furfural and the hydrogen donor molecule at the active center, thereby significantly broadening the area of ​​the catalytic transfer hydrogenation reaction of the substrate molecule and increasing the reaction rate; for example, the metal particle content in the metal organic framework catalytic material can be 0.1wt%, 0.2wt% or 0.3wt%.

[0029] In a third aspect, the present invention provides the use of the above metal organic framework catalytic material in the catalytic transfer hydrogenation reaction of furfural.

[0030] When the above technical solution is adopted, the above metal organic framework catalytic material is applied to the catalytic transfer hydrogenation reaction of furfural, and the turnover frequency value of furfural reaches 150~430h -1 , which is at least 2 to 8 times higher than existing solid catalysts.

[0031] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with specific embodiments, but the content of the present invention is not limited to the following embodiments.

[0032] Unless otherwise specified, the raw materials used in the following examples are commercially available. Example 1

[0033] This embodiment provides a method for preparing a metal organic framework catalytic material embedded with metal particles, comprising: S100, obtaining a cobalt (Co) disc and a nickel (Ni) disc, wherein the diameter of the cobalt disc and the nickel disc are 2 cm and the thickness is 1 cm; S200, placing the cobalt disc in 3 mL of N,N-dimethylformamide, and irradiating the cobalt disc with a pulsed unfocused laser beam under ultrasonic conditions to obtain a cobalt monometallic precursor solution with a cobalt content of 0.1 wt%, which is recorded as Co(DMF); The nickel disc was placed in 3 mL of N,N-dimethylformamide, and a pulsed unfocused laser beam was used to irradiate the nickel disc to obtain a nickel single metal precursor solution with a nickel content of 0.1 wt%, which was recorded as Ni(DMF); Among them, the temperature of N,N-dimethylformamide is -15 o C, the frequency of ultrasound is 20kHz, the output wavelength of the pulsed unfocused laser beam is 1064nm, the pulse frequency is 20Hz, the output spot diameter is 5mm, and the irradiation energy density of the laser beam is 500mJ / cm 2 , irradiation time is 10 minutes; S300, mixing the cobalt single metal precursor solution and the nickel single metal precursor solution in step S200 to obtain a cobalt-nickel multimetal precursor solution, denoted as CoNi(DMF); S400, measuring 12 mL of the cobalt-nickel multimetal precursor solution in step S300, adding 80 mg of zirconium chloride (ZrCl4) and 100 mg of 2-aminoterephthalic acid to the cobalt-nickel multimetal precursor solution, ultrasonically treating for 10 minutes to mix the components evenly, then adding 1.5 mL of glacial acetic acid and 300 μL of ultrapure water, continuing the ultrasonic treatment for 10 minutes, and then placing in an oven at 120° C. for solvothermal reaction for 24 hours; After the reaction is completed, the mixture is cooled to room temperature, washed, and then solid powder is collected. The solid powder is a metal organic framework catalytic material, denoted as CoNi@MOF. The cobalt content in the metal organic framework catalytic material is 0.1wt%, and the nickel content is 0.1wt%. Example 2

[0034] This embodiment provides a method for preparing a metal organic framework catalytic material embedded with metal particles, comprising: S100, obtaining a cobalt (Co) disc and a nickel (Ni) disc, wherein the diameter of the cobalt disc and the nickel disc are 2 cm and the thickness is 1 cm; S200, placing the cobalt disc in 3 mL of N,N-dimethylformamide, and irradiating the cobalt disc with a pulsed unfocused laser beam under ultrasonic conditions to obtain a cobalt monometallic precursor solution with a cobalt content of 0.2 wt%, which is recorded as Co(DMF); The nickel disc was placed in 3 mL of N,N-dimethylformamide, and a pulsed unfocused laser beam was used to irradiate the nickel disc to obtain a nickel single metal precursor solution with a nickel content of 0.2 wt%, which was recorded as Ni(DMF); Among them, the temperature of N,N-dimethylformamide is 0 o C, the frequency of ultrasound is 40kHz, the output wavelength of the pulsed unfocused laser beam is 1064nm, the pulse frequency is 40Hz, the output spot diameter is 10mm, and the irradiation energy density of the laser beam is 1400mJ / cm 2 , irradiation time is 5 minutes; S300, mixing the cobalt single metal precursor solution and the nickel single metal precursor solution in step S200 to obtain a cobalt-nickel multimetal precursor solution, denoted as CoNi(DMF); S400, measuring 6 mL of the cobalt-nickel multimetal precursor solution in step S300, adding 60 mg of zirconium chloride (ZrCl4) and 80 mg of 2-aminoterephthalic acid to the cobalt-nickel multimetal precursor solution, ultrasonically treating for 30 minutes to mix the components evenly, then adding 1 mL of glacial acetic acid and 100 μL of ultrapure water, continuing the ultrasonic treatment for 30 minutes, and then placing the solution in an oven at 100° C. for solvothermal reaction for 24 hours; the frequency of the ultrasonic treatment is 30 kHz; After the reaction is completed, the mixture is cooled to room temperature, washed, and then solid powder is collected. The solid powder is a metal organic framework catalytic material, denoted as CoNi@MOF. The cobalt content in the metal organic framework catalytic material is 0.2wt%, and the nickel content is 0.2wt%. Example 3

[0035] This embodiment provides a method for preparing a metal organic framework catalytic material embedded with metal particles, comprising: S100, obtaining a cobalt (Co) disc and a nickel (Ni) disc, wherein the diameter of the cobalt disc and the nickel disc are 2 cm and the thickness is 1 cm; S200, placing the cobalt disc in 3 mL of N,N-dimethylformamide, and irradiating the cobalt disc with a pulsed unfocused laser beam under ultrasonic conditions to obtain a cobalt monometallic precursor solution with a cobalt content of 0.3 wt%, which is recorded as Co(DMF); The nickel disc was placed in 3 mL of N,N-dimethylformamide, and a pulsed unfocused laser beam was used to irradiate the nickel disc to obtain a nickel single metal precursor solution with a nickel content of 0.3 wt%, which was recorded as Ni(DMF); Among them, the temperature of N,N-dimethylformamide is -10 o C, the frequency of ultrasound is 30kHz, the output wavelength of the pulsed unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the output spot diameter is 8mm, and the irradiation energy density of the laser beam is 1000mJ / cm 2 , irradiation time is 8 minutes; S300, mixing the cobalt single metal precursor solution and the nickel single metal precursor solution in step S200 to obtain a cobalt-nickel multimetal precursor solution, denoted as CoNi(DMF); S400, measuring 8 mL of the cobalt-nickel multimetal precursor solution in step S300, adding 70 mg of zirconium chloride (ZrCl4) and 90 mg of 2-aminoterephthalic acid to the cobalt-nickel multimetal precursor solution, ultrasonically treating for 20 minutes to mix the components evenly, then adding 1 mL of glacial acetic acid and 100 μL of ultrapure water, continuing the ultrasonic treatment for 20 minutes, and then placing in an oven at 120° C. for solvothermal reaction for 12 hours; the frequency of the ultrasonic treatment is 30 kHz; After the reaction is completed, the mixture is cooled to room temperature, washed, and then solid powder is collected. The solid powder is a metal organic framework catalytic material, denoted as CoNi@MOF. The cobalt content in the metal organic framework catalytic material is 0.3wt%, and the nickel content is 0.3wt%. Example 4

[0036] This embodiment provides a method for preparing a metal organic framework catalytic material embedded with metal particles, comprising: S100, obtaining a cobalt (Co) disc and a nickel (Ni) disc, wherein the diameter of the cobalt disc and the nickel disc are 2 cm and the thickness is 1 cm; S200, placing the cobalt disc in 3 mL of N,N-dimethylformamide, and irradiating the cobalt disc with a pulsed unfocused laser beam under ultrasonic conditions to obtain a cobalt monometallic precursor solution with a cobalt content of 0.3 wt%, which is recorded as Co(DMF); The nickel disc was placed in 3 mL of N,N-dimethylformamide, and a pulsed unfocused laser beam was used to irradiate the nickel disc to obtain a nickel single metal precursor solution with a nickel content of 0.3 wt%, which was recorded as Ni(DMF); Among them, the temperature of N,N-dimethylformamide is -10 o C, the frequency of ultrasound is 30kHz, the output wavelength of the pulsed unfocused laser beam is 1064nm, the pulse frequency is 30Hz, the output spot diameter is 8mm, and the irradiation energy density of the laser beam is 1000mJ / cm 2 , irradiation time is 8 minutes; S300, mixing the cobalt single metal precursor solution and the nickel single metal precursor solution in step S200 to obtain a cobalt-nickel multimetal precursor solution, denoted as CoNi(DMF); S400, measuring 8 mL of the cobalt-nickel multimetal precursor solution in step S300, adding 70 mg of ferric chloride (FeCl3) and 90 mg of 2-hydroxyterephthalic acid to the cobalt-nickel multimetal precursor solution, ultrasonically treating for 20 minutes to mix the components evenly, then adding 1 mL of glacial acetic acid and 100 μL of ultrapure water, continuing the ultrasonic treatment for 20 minutes, and then placing in an oven at 120° C. for solvothermal reaction for 12 hours; the frequency of the ultrasonic treatment is 30 kHz; After the reaction is completed, the mixture is cooled to room temperature, washed, and then solid powder is collected. The solid powder is a metal organic framework catalytic material, denoted as CoNi@MOF. The cobalt content in the metal organic framework catalytic material is 0.3wt%, and the nickel content is 0.3wt%.

[0037] The above examples respectively prepared metal organic framework catalytic materials CoNi@MOF with different catalytic properties, which will be described in detail in Example 1 below. Figure 1 It can be seen that the present invention first uses a liquid phase pulse laser to prepare Co(DMF) and Ni(DMF), and finally successfully embeds Co and Ni metal particles into the MOF material in situ; specifically, Figure 1 In the process, a laser beam is irradiated on a metal target to obtain a single metal precursor solution (nanocolloid), and then a multi-metal precursor solution (active metal solution) is synthesized. Metal salts and organic ligands are added to the multi-metal precursor solution for a solvothermal reaction, and then the metal organic framework catalytic material (CoNi@MOF) of the present invention is obtained by in-situ self-assembly. Figure 2 and Figure 3 It can be seen that the Co(DMF) and Ni(DMF) of Example 1 have the Tyndall phenomenon, indicating that both Co(DMF) and Ni(DMF) are colloidal solutions, and further illustrating that the Co and Ni nanoclusters are confined in the DMF solvent with extremely small sizes; Figure 4 It can be seen that after the metal Co and Ni are embedded in the MOF material, the color of the MOF material changes from light yellow to dark yellow, which further illustrates that the Co and Ni metals are successfully implanted into the MOF material. Figure 4 Figure a is the MOF material UiO-66-NH2, Figure b is Co@UiO-66-NH2 obtained by implanting Co metal particles into MOF material, Figure c is Ni@UiO-66-NH2 obtained by implanting Ni metal particles into MOF material, and Figure d is the metal organic framework catalytic material Co1Ni1@MOF, where the mass ratio of Co to Ni in Co1Ni1@MOF is 1:1. Figure 5It can be seen that the metal organic framework catalytic material CoNi@MOF still maintains the regular octahedral structure of the MOF material, with a size between 100 and 200 nm. At the same time, the element distribution diagram also shows that the Co and Ni elements are uniformly dispersed in the MOF material. Specifically, Figure 5 In the figure, Figure a is a SEM image of MOF at the micrometer scale, Figure b is a SEM image of Co1Ni1@MOF at low resolution, Figure c is a superimposed SEM image of C, N, Zr, Co and Ni elements, Figure d represents the distribution of carbon (C) elements in CoNi@MOF, Figure e represents the distribution of oxygen (O) elements in CoNi@MOF, Figure f represents the distribution of nitrogen (N) elements in CoNi@MOF, Figure g represents the distribution of zirconium (Zr) elements in CoNi@MOF, Figure h represents the distribution of cobalt (Co) elements in CoNi@MOF, and Figure i represents the distribution of nickel (Ni) elements in CoNi@MOF. Figure 6 It can be seen that the size of Co and Ni nanoparticles loaded by MOF materials is 1~5nm. At the same time, the element distribution diagram also shows that Co and Ni particles are uniformly dispersed in MOF materials, indicating that Co and Ni are uniformly embedded in the MOF skeleton with extremely small sizes. Figure 6 In the figure, Figure a shows a transmission electron microscope (TEM) schematic diagram of CoNi@MOF in Example 1, Figure b shows the distribution of oxygen (O) elements in CoNi@MOF, Figure c shows the distribution of zirconium (Zr) elements in CoNi@MOF, Figure d shows the distribution of cobalt (Co) elements in CoNi@MOF, and Figure e shows the distribution of nickel (Ni) elements in CoNi@MOF.

[0038] After the metal organic framework catalytic material CoNi@MOF is prepared in the above embodiment, it can be used in the catalytic transfer hydrogenation reaction of furfural. Figure 7 ,from Figure 7 It can be seen that the in-situ embedded CoNi@MOF has a higher turnover frequency (TOF) value than Co@MOF, Ni@MOF, and post-loaded Co / MOF, Ni / MOF, and CoNi / MOF; in particular, the TOF value of the optimized Co1Ni1@MOF is as high as 430h -1 , much higher than other types of catalysts.

[0039] In the description of the above embodiments, specific features, structures, materials or characteristics may be combined in a suitable manner in any one or more embodiments or examples.

[0040] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a metal organic framework catalytic material embedded with metal particles, characterized in that: include: Obtain a metal target; The metal target sheet is placed in N,N-dimethylformamide, and a pulsed laser beam is used to irradiate the metal target sheet under ultrasonic conditions to obtain a single metal precursor solution having a metal content of 0.05-0.4 wt %; Mixing at least two of the single metal precursor solutions to obtain a multi-metal precursor solution; After uniformly dispersing metal salts and organic ligands in the multi-metal precursor solution, glacial acetic acid and ultrapure water are added, and solvent thermal treatment is performed at a temperature of 100-120° C. for 12-24 hours. After cooling, a metal organic framework catalytic material is obtained.

2. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 1, characterized in that: The mixing of at least two single metal precursor solutions comprises: At least two of the single metal precursor solutions are mixed in equal volumes.

3. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 2, characterized in that: The metal target pieces include cobalt target pieces and nickel target pieces.

4. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 3, characterized in that: In the process of irradiating the metal target sheet with a pulsed laser beam, the pulsed laser beam comprises a pulsed unfocused laser beam; The output wavelength of the pulsed laser beam is 1064nm, the pulse frequency is 20-40Hz, the output spot diameter is 5-10mm, and the irradiation energy density of the laser beam is 500-1400mJ / cm 2 The irradiation time is 5 to 10 minutes.

5. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 4, characterized in that: In the process of irradiating the metal target sheet with a pulsed laser beam, the temperature of N,N-dimethylformamide is -15 to 0 o C, the frequency of ultrasound is 20~40kHz.

6. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 5, characterized in that: The metal salts include zirconium chloride, ferric chloride and hydrated copper nitrate; and / or, The organic ligands include 2-aminoterephthalic acid, terephthalic acid and 2-hydroxyterephthalic acid.

7. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 6, characterized in that: The mass ratio of the metal salt to the organic ligand is 1:(1-2).

8. The method for preparing a metal organic framework catalytic material embedded with metal particles according to claim 7, characterized in that: The method of uniformly dispersing metal salts and organic ligands in the multi-metal precursor solution comprises: 60-80 mg of metal salt and 80-100 mg of organic ligand are dissolved in 6-12 mL of the multi-metal precursor solution.

9. A metal organic framework catalytic material, characterized in that: The catalyst is prepared by the method for preparing a metal organic framework catalytic material embedded with metal particles according to any one of claims 1 to 8, wherein the metal particle content in the metal organic framework catalytic material is 0.1 to 0.3 wt %.

10. Use of the metal organic framework catalytic material according to claim 9 in catalytic transfer hydrogenation of furfural.

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